Classifications

• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
  • C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
  • C09K11/08—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials
  • C09K11/87—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing platina group metals
• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
  • C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
  • C09K11/08—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials
  • C09K11/87—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing platina group metals
  • C09K11/873—Chalcogenides
• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
  • C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
  • C09K11/08—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials
  • C09K11/77—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing rare earth metals
  • C09K11/7743—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing rare earth metals containing terbium
  • C09K11/77492—Silicates

Definitions

• the invention relates to the technical field of luminescent materials, in particular to a silicate luminescent material and a preparation method thereof. Background technique
• the fluorescent materials used in current field emission devices are mainly those used in conventional cathode ray tubes and projection television tubes, oxide series and oxide series luminescent materials.
• the luminescence brightness is higher and has certain conductivity, but it is easily decomposed under the bombardment of large beam electron beams, releasing the elemental sulfur "poisoning" cathode tip, and generating other The precipitate covers the surface of the luminescent material, which reduces the luminous efficiency of the luminescent material and shortens the service life of the field emission device.
• the value of X ranges from 0.02 ⁇ x ⁇ 0.10.
• the value of y ranges from lx l0_ 5 ⁇ y 5 ⁇ 10_ 3 .
• the above silicate luminescent material effectively overcomes the structural defects of the titanate luminescent material by doping the metal particles, reduces the probability of non-radiative transition, and makes the luminous efficiency of the titanate luminescent material under the same excitation condition extremely great. Raise, the wavelength of the emitted light does not change.
• the silicate luminescent material has good stability, overcomes the defects of easy decomposition of sulfide and sulfur oxide series luminescent materials, and can be used in field emission devices instead of sulfide and sulfur oxide series luminescent materials.
• a method for preparing a silicate luminescent material comprising the steps of:
• a molar ratio of M to Si ratio y of the element is added to the airgel Si0 2 M salt solution, the mixture was stirred at 50 ⁇ 75 ° C were mixed solution hook, the mixed solution was sonicated, The sonicated solution is dried at 60 to 150 ° C, and the mixture obtained after drying is uniformly ground and calcined at 600 to 1200 ° C to obtain a Si 2 aerogel containing M ions, wherein
• the M is at least one of Ag, Au, Pt, Pd, and Cu metal nanoparticles, and the range of y is 0 ⁇ y ⁇ lxl (T 2 ; according to the molar ratio of Li, Ca, Tb, and Si elements
• For the ratio of 2: ( 1 -x) :x: 1 weigh out the Li compound, the Ca compound and the Tb compound, and the M 2 -containing SiO 2 aerogel, and grind and mix uniformly to obtain a mixture, wherein X is taken
• the value range is 0 ⁇
• the mixture is subjected to calcination treatment at 500 to 1000 ° C, and the mixture is placed in a reducing atmosphere at 800 to 1200 ° C for reduction treatment, and then the reduced mixture is cooled to room temperature. Grinding to obtain the silicate luminescent material having the chemical formula of Li 2 Ca 1 ⁇ c SiO 4 :Tb x ,M y , wherein Tb and M are doped in Li 2 Ca 1-x SiO 4 , and Tb and M are doped particles.
• the solute in the salt solution of M is at least one of HAuCl 4 , H 2 PtCl 6 , AgN 0 3 , PdCl 2 —2H 2 0 and Cu(N0 3 ) 2 , and the solvent is ethanol.
• the concentration of the M salt solution is 5x lO_ 6 ⁇ lx lO_ 2 mol / L.
• the Li compound is an oxide, a carbonate, a nitrate, or a vinegar of Li.
• the Tb compound is an oxide, a carbonate, a nitrate, an acetic acid of Tb Salt or oxalate.
• the reducing atmosphere is a CO reducing atmosphere or a H 2 reducing atmosphere or a mixed reducing atmosphere having a volume fraction of 95% N 2 and 5% 3 ⁇ 4.
• X has a value range of 0.02 ⁇ x ⁇ 0.10; y has a value range of lxl (T 5 ⁇ y 5xl (T 3 ) .
• the method for preparing the above silicate luminescent material firstly adsorbs metal ions by a SiO 2 aerogel to obtain a SiO 2 aerogel containing metal ions, and then, a compound of Li, Ca, and Tb, and Si0 containing a metal ion.
• 2 aerogel is used as raw material to reduce metal ions into metal element under reducing atmosphere, ie, silicate luminescent material with chemical formula of Li 2 Ca 1 ⁇ c Si0 4 :Tb x ,M y is prepared, preparation process tube Single, low cost, non-polluting, easy to control reaction, suitable for industrial production, the resulting silicate luminescent materials have high luminosity efficiency and good stability, and have broad application prospects in field emission devices.
• 1 is a flow chart showing a method of preparing a silicate luminescent material according to an embodiment
• FIG. 2 is a comparison diagram of luminescence light of a luminescent material prepared in Example 3 under a cathode ray excitation at a voltage of 1.5 kV, wherein curve 1 is a metal doped Li 2 Ca 9 oSi0 4 : Tb i o, Ag 2.
• the luminescence spectrum of the 5xl o-4 luminescent material, and the curve 2 is the luminescence spectrum of the undoped metal Li Cao. oSiO ⁇ Tbo.K) luminescent material.
• the silicate luminescent material of one embodiment has a chemical formula of Li 2 Ca 1 ⁇ c Si0 4 :Tb x ,M y .
• Tb and M are doped in Li 2 Ca 1-x SiO 4
• Tb and M are doped particles.
• M is at least one of Ag, Au, Pt, Pd, and Cu metal nanoparticles.
• the value of X ranges from 0 ⁇ x ⁇ 0.2.
• y is the molar ratio of M to Si elements.
• the value of y ranges from 0 ⁇ y ⁇ lxl (T 2 .
• the value range of X may also be 0.02 ⁇ x ⁇ 0.10, and the range of y may also be lxl (T 5 ⁇ y ⁇ 5xl (T 3 ) .
• the embodiment further provides a method for preparing a silicate luminescent material, as shown in FIG. 1, which includes the following steps:
• Step S110 adding a SiO 2 aerogel to the salt solution of M according to the ratio of molar ratio of M to Si, and mixing and stirring at 50-75 ° C to obtain a mixed solution, and then performing the mixed solution.
• the mixture is sonicated, and the mixed solution after sonication is dried at 60 to 150 ° C.
• the mixture obtained after drying is uniformly ground and calcined at 600 to 1200 ° C to obtain a Si 2 aerogel containing M ions.
• M is at least one of Ag, Au, Pt, Pd and Cu metal nanoparticles.
• the value of y ranges from 0 ⁇ y ⁇ lxl (T 2 .
• the solute in the salt solution of M is at least one of HAuCl 4 , H 2 PtCl 6 , AgN0 3 , PdCl 2 -2H 2 0 and Cu(N0 3 ) 2 . species, and the solvent is ethanol.
• the concentration range of the M salt solution is 5x 10- 6 ⁇ lx l0- 2 mol / L.
• Step S120 weighing the Li compound, the Ca compound and the Tb compound, and the SiO 2 aerogel containing the M ion according to a molar ratio of Li, Ca, Tb and Si elements of 2:(lx):x:l, grinding Mix well and obtain a mixture.
• the Li compound is an oxide, carbonate, nitrate, acetate or oxalate of Li.
• Ca compound An oxide, carbonate, nitrate, acetate or oxalate of Ca.
• the Tb compound is an oxide, carbonate, nitrate, acetate or oxalate of Tb.
• Step S130 the mixture is placed at 500 ⁇ 1000 °C for calcination treatment, and then the mixture is placed in a reducing atmosphere at 800 ⁇ 1200 °C for reduction treatment, and then the reduced mixture is cooled to room temperature. Grinding to obtain a silicate luminescent material having a chemical formula of Li 2 Ca 1 ⁇ c SiO 4 :Tb x ,My. Wherein Tb and M are doped in Li 2 Ca 1-x SiO 4 , and Tb and M are doped particles.
• the reducing atmosphere may be a CO reducing atmosphere or a H 2 reducing atmosphere or a mixed reducing atmosphere having a volume fraction of 95% N 2 and 5% 3 ⁇ 4.
• the silicate luminescent material effectively overcomes the structural defects of the titanate luminescent material by doping the metal particles, reduces the probability of non-radiative transition, and makes the luminous efficiency of the titanate luminescent material under the same excitation condition extremely great. Raise, the wavelength of the emitted light does not change.
• the silicate luminescent material has good stability, overcomes the defects of easy decomposition of sulfide and sulfur oxide series luminescent materials, and can replace the sulphide and sulfur oxide series luminescent materials in field emission devices.
• the method for preparing the silicate luminescent material firstly adsorbing metal ions by a SiO 2 aerogel, To a SiO 2 aerogel containing a metal ion, and then using a compound of Li, Ca, and Tb and a SiO 2 aerogel containing a metal ion as a raw material, reducing the metal ion to a metal element under a reducing atmosphere, that is, preparing A silicate luminescent material having a chemical formula of Li 2 Ca 1 ⁇ c SiO 4 :Tb x ,M y is obtained, and the preparation process is simple, low in cost, non-polluting, easy to control, and suitable for industrial production, and the obtained silicic acid Salt luminescent materials have high luminescence efficiency and good stability, and have broad application prospects in field emission devices.
• the test of the different compositions of the silicate luminescent materials, the preparation method thereof, and the properties thereof will be described below in conjunction with specific examples.
• composition of the silicate luminescent material of this embodiment is Li 2 Ca 85 Si0 4 : Tb i5 , Au lxl ( ) -2 , and the preparation process is as follows:
• the mixture prepared above is placed in an agate mortar and fully ground to a mixing hook; then the powder is transferred to a corundum crucible, heat treated at 500 ° C for 15 h in a muffle furnace; and then reduced in a tube furnace at a C atmosphere. after sintering at 1000 ° C 2h, Au 3+ is reduced to about to elemental Au; cooled to room temperature, the sample was ground into a powder, to obtain the Au-doped Li 2 Cao 85 Si0 4: Tbo 15,.. Au lxl o- 2 luminescent material.
• composition of the silicate luminescent material of this embodiment is , the preparation process is as follows:
• Si0 2 aerogels were dissolved in 6mL concentration of 5 ⁇ 10_ 3 mol / L chloroplatinic acid (H 2 PtCl 6) in ethanol and the resulting mixture was stirred for 3 h at 50 ° C, Then, it was sonicated for 10 min, and then dried at 60 ° C. The sample obtained after drying was uniformly ground and then calcined at 600 ° C for 4 h to obtain Pt 4+. Si0 2 aerogel.
• H 2 PtCl 6 chloroplatinic acid
• Li 2 CO 3 lithium carbonate
• CaCO 3 0.3924 g of 4 carbonic acid
• Tb 2 (C0 3 ) 3 cesium carbonate
• 0.2404 g of the above-prepared Si 2 2 containing Pt 4+ were weighed. Aerogel, preparation of the mixture.
• the mixture prepared above is placed in an agate mortar and fully ground to a mixing hook; then the powder is transferred to a corundum crucible, heat treated at 1000 ° C for 2 h in a muffle furnace; and then reduced in a CO furnace at a CO atmosphere. After sintering at 1200 ° C for 0.5 h, that is, Pt 4+ is reduced to Pt elemental; after cooling to room temperature, the obtained sample is ground into a powder to obtain P 2 -doped Li 2 Cao. 98 Si0 4 : Tbo. 2 , Pt 5xl () - 3 luminescent materials.
• the mixture prepared above was placed in an agate mortar and thoroughly ground to a homogenous hook; then the powder was transferred to a corundum crucible, heat treated at 600 ° C for 4 h in a muffle furnace; and 95% N in a tube furnace.
• 2 + 5% 3 ⁇ 4 (volume fraction) in a mixed reducing atmosphere is sintered at 1000 ° C for 4 h, that is, after Ag + is reduced to Ag element; after cooling to room temperature, the obtained sample is ground into a powder to obtain Ag-doped Li 2 Ca 0 . 90 SiO 4 : Tb 0 . 10 , Ag 2 . 5 ⁇ 10 ⁇ 4 luminescent material.
• the doped metal Ag prepared in this embodiment is the doped metal Ag prepared in this embodiment.
• composition of the silicate luminescent material of this embodiment is Li 2 Ca 8() SiO 4 : Tb 2 (), Pd lxl () - 5 , and the preparation process is as follows:
• the mixture prepared above is placed in an agate mortar and thoroughly ground to a homogenous hook; then the powder is transferred to a corundum crucible, heat treated at 700 ° C for 5 h in a muffle furnace; and in a tubular furnace at H 2 Sintering at 800 ° C for 6 h in a reducing atmosphere, that is, Pd 4+ is reduced to Pd elemental; after cooling to room temperature, the obtained sample is ground into a powder to obtain Pd -doped Li 2 Cao. 8 oSi0 4 : Tbo. 2 o, Pd lxl o- 5 luminescent material.
• composition of the silicate luminescent material of this embodiment is Li 2 Ca 95 Si0 4 : Tb () 5 , Cu lxl (H , the preparation process is as follows:
• Si0 2 aerogel 0.3606 g of Si0 2 aerogel was weighed and dissolved in 12 mL of a solution of copper nitrate (Cu(N0 3 ) 2 ) having a concentration of 5 ⁇ 10_ 5 mol/L, and the obtained mixed solution was stirred at 70 ° C for 1 h. Then, it was ultrasonicated for 10 min, and then dried at 70 ° C. The sample obtained after drying was ground and hooked, and calcined at 800 ° C for 2 h to obtain a SiO 2 aerogel containing Cu 2+ .
• Cu(N0 3 ) 2 copper nitrate
• composition of the silicate luminescent material of this embodiment is Li 2 Ca 88 Si0 4 : Tb i2 , Ag 5 xl () -4 , and the preparation process is as follows:
• the mixture prepared above is placed in an agate mortar and fully ground to a homogenous hook; then the powder is transferred to a corundum crucible, heat treated at 500 ° C for 10 h in a muffle furnace; and then in a tubular furnace at H 2 After sintering at 1100 ° C for 3 h in a reducing atmosphere, the Ag + is reduced to Ag element; after cooling to room temperature, the obtained sample is ground into a powder to obtain Ag-doped Li 2 Ca 88 Si0 4 : Tb i2 , Ag 5 xl () -4 luminescent material.
• composition of the silicate luminescent material of this embodiment is Li Cao ⁇ SiO ⁇ Tbo.os Ago.s/Auo. ⁇ . xK ⁇ , and the preparation process is as follows:
• the mixture prepared above was placed in an agate mortar and thoroughly ground to a homogenous hook; then the powder was transferred to a corundum crucible, heat treated at 700 ° C for 8 h in a muffle furnace; and 95% N in a tube furnace.
• the obtained sample is ground into a powder to obtain I ⁇ Cao ⁇ SiO ⁇ Tbo.os Ago.s/Auo. ⁇ xK luminescent material doped with Ag and Au .

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• 2012
  • 2012-10-31 CN CN201280076460.1A patent/CN104736666A/zh active Pending
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